Durable Perovskite Solar Cells with 24.5% Average Efficiency: The Role of Rigid Conjugated Core in Molecular Semiconductors

Abstract

AbstractEfficient and robust n‐i‐p perovskite solar cells necessitate superior organic hole‐transport materials with both mechanical and electronic prowess. Deciphering the structure–property relationship of these materials is crucial for practical perovskite solar cell applications. Through direct arylation, two high glass transition temperature molecular semiconductors, DBC‐ETPA (202 °C) and TPE‐ETPA (180 °C) are synthesized, using dibenzo[g,p]chrysene (DBC) and 1,1,2,2‐tetraphenylethene (TPE) tetrabromides with triphenylene–ethylenedioxythiophene‐dimethoxytriphenylamine (ETPA). In comparison to spiro‐OMeTAD, both semiconductors exhibit shallower HOMO energy levels, resulting in increased hole densities (generated by air oxidation doping) and accelerated hole extraction from photoexcited perovskite. Experimental and theoretical studies highlight the more rigid DBC core, enhancing hole mobility due to reduced reorganization energy and lower energy disorder. Importantly, DBC‐ETPA possesses a higher cohesive energy density, leading to lower ion diffusion coefficients and higher Young's moduli. Leveraging these attributes, DBC‐ETPA is employed as the primary hole‐transport layer component, yielding perovskite solar cells with an average efficiency of 24.5%, surpassing spiro‐OMeTAD reference cells (24.0%). Furthermore, DBC‐ETPA‐based cells exhibit superior operational stability and 85 °C thermal storage stability.